Black azo dye.



NITE l Prion.

STATES Artur GEORG KOERNER, OF LUDW'IGSHAFEN, GERMANY, ASSIGNOR TO THEBADISCHE ANILIN AND SODA FABRIK, OF SAME PLACE.

BLACK A DYE.

-'SPEGIFICATION forming part of Letters Patent No. 638,127, datedNovember @8, 1899.

Application filed June 24, 1899. Serial No. 721,766. (SpeoimensJ To allwhom it may concern:

Be it known that I, GEORG KOERNER, doctor of philosophy, a subject ofthe Grand Duke of Hesse, residing at Ludwigshafen-on-the- Rhine, in theKingdom of Bavaria, Germany, have invented new and useful Improvementsin the Manufacture of New Black Substantive Azo Coloring-Matters forCotton, (for which application has been filed in Germany Decemher 9,1898, No. B 23,886,) of which the following is a specification.

My invention relates to thenlanufacture of a new class of blacksubstantive azo coloringmatters suitable for dyeing cotton without theaid of a mordant.

My new coloring-matters are derived from 1.8 amido-naphthol t or 5monosulfoacid. They are obtained from the said acids by the suitablecombination of two tetrazo residues therewith. The said tetrazo residuesmay be regarded as tetrazo compounds, of which one diazo group isalready combined with a component, while the second azo group remainsand eventually combines with the amidonaphthol-sulfoacid. Not all suchazo dyes which can be obtained by the combination of such tetrazoresidues with the said amidonaphthol-sulfoacids are valuable blacksubstantive coloring-matters, such as I desire to claim. In order toobtain my new valuable coloring-matters, the tetrazo residues must besuitably chosen and their combination -due which contains one or morehydroxyl groups attach itself to the part of the amidonaphthol-sulfoacidresidue which contains the hydroxyl, then the particular blackcoloringmatters of excellent quality which I desire to claim areobtained.

My new coloring'matters therefore possess the following general formula:

in which N:\'XN:NA is a tetrazo residue containing one or more basicgroups and -N:N.YN:NB is a tetrazo residue containing one or morehydroxyl groups.

As an instance of a dye of my new class of dyes I mention thatpossessing the following formula:

S (4 or 5.)

In this the tetrazo residue containing the basic groups is obtained frompara-phenylenediamin-azo-meta-phenylene-diamin, and the,

which I make no claim yields when using the same quantity ofcoloring-matter only darkgreen shades on cotton.

Other members of my new class of coloringmatters are obtained ifpara-phenylene-di-i amin-azo-meta-toluylene-diamin be used as the sourceof the tetrazo residue containing the amido groups instead ofpara-phenylenediamin-azo-meta-phenylene-diamin. Also on the other hand,benzidin-azo-phenol, benzidin-azo-salicylic acid,para-phenylene-diamin-azo-phenol, or para-phenylene-diamin-azoresorcinolcan be used instead of the paraphenylene-diamin-azo-salicylic acid asthe source of the tetrazo residues containing the acid groups.

In my present application for Letters Patent I desire to claim my newprocess for the production of black substantive coloring-1n atters forcotton and the said new coloring-matters themselves generically, and,further, I claim specifically the new coloring-matter whose constitutionis above set forth in the formula.

The following example will serve to illustrate the manner in which myinvention can be carried into practical effect. Parts are by weight:

Example: Diazotize two hundred and twenty-eight (228) parts ofpara-phenylenediamin azo meta phenylene diamin in the Well-known way,using sixty-nine parts of sodium nitrite and three hundred and eighty(380) parts of hydrochloric acid (containing about thirty per cent.H-Ol.) Take such a quantity of water that about two thousand (2,000)parts of diazo solution are obtained. Run this into a suspension of twohundred and forty (2-10) parts of 1.8 amido-naphthol 4 sulfoacid insixteen thousand (16,000) parts of water and four thousand (4,000) partsof ice. After a short time add two thousand (2,000) parts ofsodium-acetate solution containing ten per cent. sodium acetate. Stirfor about five or six hours. A test portion on paper should nolongershow a yellow liquid that turns blue violet with soda. W'hen thisis the case, the production of the intermediate product may be regardedas finished. In this way the combination of the tetrazo residuecontaining the basic groups in the part of the amido-naphthol-sulfoacidmolecule containing the amido group is effected. Next add to the liquideight thousand parts of a solution of carbonate of soda (containing tenper cent. Na CO and to the liquid so obtained add a diazo solutionobtained in the well-known Way from two hundred and eighty (280) partsof para-phenylene-diamin-azo-salicylic acid, four hundred and twenty(420) parts of hydrochloric acid, (containing thirty per cent. II 01,)and sixty-nine (69) parts of sodium nitrite. Stir for twelve hours? Theformation of the coloring-matter will then be finished. Warm up to aboutto and stir in eight thousand (8,000) parts of common salt. Thecoloring-matteris precipitated. Filter, press, and dry.

In the foregoing example I have described the method of introducingtetrazo residues in the desired manner into the amido-naphtholsulfoacidby first combining in acid solution. In this way the tetrazo residueemployed is introduced into that part of the amidonaphthol-sulfoacidwhich contains the amido group, while the part containing the hydroxylgroup remains unchanged. The introduction of the second tetrazo residuecan best be ef fected by combination in alkaline solution, asillustrated; but it can also be carried in neutral or even weakly acidsolution, if desired. It is possible to first introduce the tetrazoresidue containing the hydroXyl groups into the part of theamido-naphthalene-sulfoacid containing the hydroXyl group by combination, in the first instance, in alkaline solution. Then theintroduction of the second tetrazo residue containing the amido groupscan be effected as desired; but the method illustrated by the example isthat which is recommended.

My new group of coloring-matters are all characterized by the followingproperties: They are dark-colored powders soluble in hot water and dyecotton goods giving black shades without the aid of a mordant. A dilutesolution of the coloring-matters containing one (1) part coloringmatterin about one thousand (1,000) parts of water rendered alkaline withcarbonate of soda is violet to blue in color. On treating such asolution with diazo-sulfanilic acid the coloring-matter is decomposedand the color of the solution turns toward brown.

The coloring-matter which I desire to claim specifically possesses theconstitution hereinbefore shown in the formula, and is characterized byall the generic properties appertaining to mynew group of dyes. Itsaqueous solution is reddish blue to blue, while its solution inconcentrated sulfuric acid is blue.

Now what I claim is The new coloring-matters which can be derived fromamido naphthol monosulfoacid (1. 8. 1; 1.8.5.) and a tetrazo residuecontaining one or more basic groups attached to the part of the amidonaphthol sulfoacid residue which contains the amido group, and atetrazoresidue containing one or more hydroxyl groups attached to the part ofthe amidonaphthol-sulfoacid residue which contains the hydroXyl, andwhich is characterized by dyeing cotton goods yielding black shadeswithout the aid of a mordant, and yielding a violet to blue solution inwater rendered alkaline with carbonate of soda, in which thecoloring-matter is decomposed by the addition of diazo-sulfanilic acid,all substantially as described.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

GEORG KOERNER.

Witnesses i OSCAR BALLY, 'GUSTAV L. LIOHTENBERGER.

